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V. K. Yadav et al.
Letter
Synlett
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(22) General Procedure for the Synthesis of β-Keto Sulfones 3
Enol acetate 1 (1 mmol), sulfonyl hydrazide 2 (1.5 mmol), FeCl3
(10 mol%), and THF (3 mL) were added to a flask open to the air,
and the mixture was stirred at 70 °C for 5–6 h (Scheme 2). After
completion of the reaction (monitoring by TLC), H2O (5 mL) was
added, and the mixture was extracted with EtOAc (3 × 5 mL).
The combined organic phases were dried over anhydrous
Na2SO4, filtered, and evaporated under reduced pressure. The
resulting crude product was purified by silica gel chromatogra-
phy using a mixture of hexane–EtOAc (4:1) as eluent to afford
an analytically pure sample of product 3. All the compounds 3
are known and were characterized by comparison of their spec-
troscopic data with those reported in the literature.4d,5b,19d,21
Characterization Data of Representative Compounds 3
Compound 3a:4d,5b solid; 91% yield. 1H NMR (400 MHz, CDCl3): δ
= 7.95 (d, J = 7.6 Hz, 2 H), 7.80 (t, J = 8.5 Hz, 2 H), 7.61 (t, J = 7.5
Hz, 1 H), 7.44 (t, J = 7.8 Hz, 2 H), 7.35 (d, J = 7.8 Hz, 2 H), 4.71 (s,
2 H), 2.47 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 188.27,
145.53, 135.85, 135.84, 134.43, 129.98, 129.46, 128.96, 128.73,
63.86, 21.87. MS (EI): m/z = 274 [M+]. Anal. Calcd for C15H14O3S:
C, 65.67; H, 5.14; S, 11.69. Found: C, 65.89; H, 4.93; S, 11.53.
Compound 3i:19d,21b solid; 92% yield. 1H NMR (400 MHz, CDCl3):
δ = 7.86 (d, J = 8.4 Hz, 2 H), 7.81 (d, J = 8.4 Hz, 2 H), 7.30–7.26 (m,
2 H), 7.24–7.20 (m, 2 H), 4.70 (s, 2 H), 2.44 (s, 3 H), 2.44 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 187.65, 145.38, 145.15, 136.11,
133.46, 129.70, 129.39, 129.37, 128.50, 63.56, 21.59, 21.52. MS
(EI): m/z = 288 [M+]. Anal. Calcd for C16H16O3S: C, 66.64; H, 5.59;
S, 11.12. Found: C, 66.80; H, 5.43; S, 11.39.
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Compound 3j: 4d,21a solid; 86% yield. 1H NMR (400 MHz, CDCl3):
δ = 7.91–7.87 (m, 4 H), 7.73 (t, J = 7.5 Hz, 1 H), 7.54 (t, J = 7.6 Hz,
2 H), 7.46 (d, J = 8.5 Hz, 2 H), 4.73 (s, 2 H). 13C NMR (100 MHz,
CDCl3): δ = 186.97, 141.30, 138.67, 134.51, 134.15, 130.89,
129.41, 129.38, 128.66, 63.69. MS (EI): m/z = 294, 296 [M+, M+ +
2]. Anal. Calcd for C14H11ClO3S: C, 57.05; H, 3.76; S, 10.88.
Found: C, 57.33; H, 3.89; S, 10.98.
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© Georg Thieme Verlag Stuttgart · New York — Synlett 2016, 27, 427–431